Coatings for masonry building units



. a1 purpose.

United States Patent COATINGS FOR MASONRY BUILDING UNITS This invention relates to improved coatings for masonry building units, more particularly this invention relates to a novel composition which may be utilized in coating masonry building units.

Many conventional masonry building units, such as cement block and cinder blocks, possess rough, porous and comparatively unattractive surfaces and it became apparent to the industry that such surfaces could be coated for either a decorative or a structurally function- One of the first conventional surface coats utilized on such surfaces was an ordinary paint composition but it was found extremely diflicult to produce a smooth decorative and attractive finish on these surfaces because the fluid agents in such compositions were generally absorbed into the pores of many of these type units giving the final coated surface a somewhat dissipated appearance. Some of the more conventional compositions utilized for such coating purposes have been generally inorganic in nature, for instance ceramic tiles, glass frits or ordinary cements. In many cases it has been found that these inorganic materials serve their decorative purpose, however, their overall utility is somewhat limited due to the inherent characteristics of the final surface coat that they form. Generally the final surface coats formed by such inorganic materials not only possess porosity and brittleness which are relatively poor characteristics for these type surfaces, but in many cases these final surfaces exhibit a susceptibility to either I efliorescence or metallic stain which may somewhat curtail their aesthetic vallue. In the case of the ceramic tile "surfaces it is generally necessary to use special techniques to ordinarily tool the surface. Further, in some instances it is commercially unattractive to utilize such inorganic surfaces because in many cases it has been found that only a limited size building unit may be v a moldable polyester type resin based fluid composition,

most generally extended with inorganic filler compounds, which may be cured to the solid state while in contact with the surface of a masonry building unit. The aesthetic or decorative effect of the surfaces formed from these resins is relatively good. However, it has been found that in many cases to obtain the desired aesthetic effect many of the desirable structural characteristics are impaired with the result that frequently a surface is obtained which will have a comparatively high degree of brittleness with a dow degree of impact resistance. Further indications are that during a comparatively normal life span the cleanability of such polyester surfaces becomes very poor and also during this time these surfaces undergo relatively pronounced color changes. It is known that in a number of cases where the polyester based surfaces are applied to conventional building units the weight of such unit is significantly increased due to the fact that a comparatively large amount of composition is generally required for such function and this fact alone may quite well influence the type of structural designs in which this unit will be acceptable.

We have discovered a novel composition which may be applied to masonry building units to form a surface 2,995,534 Patented Aug. 8, 1961 coating" which is not only comparatively less brittle, but it also has a relatively higher abrasion resistance and is more readily cleaned than many of the surface coatings which have been heretofore produced. The surface coatings formed from the present composition are not only more durable than the cement type masonry facings, but they also are less brittle than either ceramic or cement surface coats. It has further been found that the surface coats produced from the present composition may be ordinarily tooled, i.e.,, nailed, sawed, or a screw may be applied to them, without the utilization of special skills. Another advantage of the present composition is the fact that it forms surface facings which are comparatively more level, homogeneous, smooth, impervious, and more readily cleaned than painted masonry building units.

The composition of this invention includes a polyvinyl chloride resin based component dispersed in a fluid medium composed of two or more plasticizers one of which is polymerizable and may also include a catalytic medium to aid curing the resinous components, one or more suitable filler agents one of which is sand in substantial quantities.

Although it is generally a tendency for many vinyl compositions to exhibit more or less poor bonding characteristics, it has been found that the present composition is unique because it exhibits most generally an intimate and permanent bond between its component parts and the surface of the masonry building unit to which it is applied. It has also been found that the surface coatings produced by this composition are not only about harder, more scratch resistant and more resistant to discoloration at higher temperatures than many of the general vinyl compositions known to date, but also as determined by simulating tests the bond exhibited by the cured composition will withstand any of the normal stresses and strains which may be encountered in the average life span of a commercial building.

There are two basic requirements in the formulation of any fluid composition of the present type. It must have satisfactory flow properties for the intended method of application and it must give the desired end properties after fusion. Both of the aforesaid properties are influenced by the kind and amount of the ingredients present in the composition.

Initially all of the fluid components of the compositions are mixed in a conventional stirring vessel. One of these fluid'components is a polymerizable plasticizer. A function of this fluid plasticizer is to transform itself into a solidified mass when subjected to temperature within the curing range of the polyvinyl chloride resinous component of the composition. It has been found that this plasticizer will initially act as somewhat of a dispersant and carrier for the dry ingredients of the composition when they are added to the fluid system aiding in producing a fluid moldable mass.- Generally, this plasticizer will exert a slight degree of solvating action upon the resin when it is in the uncured state but this solvating action will substantially cease after the heating stage of the process because this plasticizer will itself polymerize to produce a solidifying matrix. The polymerizable plasticizers which may be utilized in the formulation of the present composition are the epoxy plasticizers such as diglycidyl ethers of bisphenol A (Le. bis [4-hydroxyphenyl]diinethyl methane) commercially available under the tradenameof Epon 828 produced by the Shell Company, divinyl esters such as divinyl sebacate, divinyl isosebacate, and divinyl adiphate, acrylates such as glycidyl methacrylate monomer, polyethylene glycol dimethacrylate, and polyester resin mixtures such as that of a resinous product known as Paraplex P-43 made and sold ice '3 by Rohm and Haas (believed to be a condensation product of propylene glycol and dipropylene glycol with phthalic anhydride and maleic anhydride), and a resinous product commercially known as Paraplex P-13," made and sold by the same company believed to be a condensation product of ethylene glycol and diethylene glycol with phthalic anhydride, maleic anhydride and adipic acid. We have obtained especially satisfactory results when polyethylene glycol dimethacrylate was utilized as the polymerizable plasticizer. Most generally the viscosity of this plasticizer should be between about 1 centipoise and about centipoise at 24" C. We have found that a ratio of between about 40 parts to about 80 parts by weight of polymerizable plasticizer to about 100 parts by weight of resin may be used in the present composition, but preferably we use a ratio of between about parts to about 75 parts of polymerizable plasticizer to 100 parts of resin because we have found that the desired filler carrying capacity of the system is not achieved until about 50 parts of this type of plasticizer are used in the system, but also that beyond about 75 parts the properties of the mass are not substantially improved. Optimum characteristics were obtained when a ratio of about 73.5 parts of polymerizable plasticizer to about 100 parts of resin was utilized in the composition.

Another fluid composition incorporated into the composition is a conventional plasticizing component. Due to the fact that the polymerizable plasticizer does not solvate the resin to the degree that is desired, we have utilized a conventional plasticizer to obtain the desired level of solvation. It is also a function of this type plasticizer to substantially maintain its solvating action upon the polyvinyl chloride resin at temperatures within the temperature range to which the composition is subjected. It has also been found that the use of this type plasticizer imparts a desirable degree of flexibility to the cured mass which tends to avoid a product which is susceptible to brittleness. There are a number of conventional plasticizers which may be incorporated as a component in the present composition, for instance dioctyl phthalate, trioctyl phthalate, tricresyl phthalate, tributyl phosphate, 2-ethyl hexyl diphenyl phosphate and sebacate type plasticizers such as dioctyl sebacate and dibutyl sebacate. We preferentially have utilized the phosphate type plasticizers such as 2-ethyl hexyl diphenyl phosphate because it imparts self extinguishing properties to the final cured mass. Satisfactory results may be obtained when this type plasticizer is used in the ratio of between about 17 parts to about 60 parts by weight of plasticizer to about 100 parts by weight of resin, and optimum results were obtained when the ratio utilized was about 19 parts plasticizer to about 100 parts resin. If a quantity of plasticizer is utilized which is below about 17 parts the mass will not cure as desired. It has been found that if the cured mass possesses a high degree of brittleness that it may be due to the insutficient fluidity of the system during the molding process, however, if more than about 60 parts of plasticizer is used the desired durability and toughness of the final coat is materially reduced.

Other fluid components which may be incorporated during the initial mixing stage of the formulation include viscosity depressants. The initial viscosity of the present fluid composition is largely dependent upon the viscosity of the plasticizing components themselves, but on aging it is the tendency of some plasticizers to solvate or swell the resinous particles at room temperature and the viscosity of the system would rise accordingly. To aid in the quality control of the fluid mass and to enhance its shelf life we have added a viscosity depressant to the fluid system when it is desired to store the same for any length of time. There are a number of depressants which may be utilized in the present composition with the basic requirements being that it must be compatible with the other components of the composition, for instance,

either of the following may be used as a viscosity depressant, i.e., mixtures of glycolic esters of caprilic and caproic acid, such as that commercially available under the tradename of Drews SC" from the E. F. Drew Company which is thought to be a mixture of triethylene glycol dicaprate and triethylene glycol dicaprylate, tetraethylene glycol pelargonate, Paraplex G-60, and Paraplex G- 62, commercially available from the Rohm and Haas Company, and believed to be epoxidized triglycerides, polyglycol adipate, and a soya oil, containing about 65% lecithin, xylene, and 1,l,1-trichloroethane. Satisfactory product results have been obtained when a mixture of glycolic esters of caprylic and caproic acid, such as that commercially available under the tradename of Drew's SC from the E. F. Drew Company which is thought to be a mixture of triethylene glycol di-caprate and triethylene glycol di-caprylate, were used as viscosity depressants in the present system. When any one of the aforesaid depressants was used it was found that such agent would not only act as a depressant but also as a carrier for the polyvinyl chloride resin and fillers materially aiding in the maintenance of the fluidity of the system thereby allowing the economical reduction in the amount of total plasticizer fluids which may be used for this function. We have found that a ratio of between about 1 part and about 10 parts by weight of depressant to about parts by weight of resin may be utilized, but we have preferentially utilized a ratio of about 4 parts of depressant to about 100 parts of resin because optimum product characteristics were obtained in this range.

Also, a free radical producing catalyst is incorporated in the present composition to aid in substantially curing the polymerizable plasticizer during the heating stage of the process. We preferentially utilized t-butyl perbenzoate as the catalyst when polyethylene glycol dimethacrylate is used as the polymerizable plasticizer in the composition because not only is optimum pot life facilitated at room temperature but also substantially uniform cure properties are obtained after polymerization of both the resinous component and the plasticizer. There are other suitable catalysts which may be utilized depending upon the specific polymerizable plasticizer and these will be most generally apparent to those in the polymer art, for instance the following: ditertiary butyl peroxide; benzoyl peroxide; alpha,alpha,azo-bis iso butyronitrile; methyl ethyl ketone peroxide and dicumyl peroxide. The catalyst may be present in the ratio of between about 0.73 part to about 6 parts of catalyst to about 100 parts of resin with the optimum curing results being obtained when the ratio is about 1.25 parts of catalyst to about 100 parts of resin.

At this point in the formulation we preferentially stir in the fillers, pigments and inhibitors which are desired to be incorporated into the composition, but these type ingredients may be incorporated at either an earlier or later stage of the formulation procedure. The function of the fillers is primarily to give bulk to the fluid composition but it is also known that certain fillers may impart desirable characteristics to the final surface coat, for instance increased hardness, enhanced scratch resistance, and durability to the finished surface. It may be seen that if the overall bulk of the composition is increased by the addition of inexpensive fillers that the ratio of the weight of the comparatively expensive resin to the weight of the total mass is relatively decreased, enhancing the commercial attractiveness of such coating composition. The addition of a filler to a fluid composition of the present type most generally increases-its viscosity because the quantity of plasticizers used to wet the fillers is unavailable to contribute to the fluidity of the resinous mass. For the aforesaid reason, fillers should be chosen with some consideration for their plasticizer wetting requirement. Some of the conventional fillers which have been used in the presenttype fluid composition have been calcium carbonates, conventional clays, surface treated clays,

ethylene .particles in water, said polyethylene particles hving a size less than microns, made in accordance with the method defined in claim 2.

4. The method of increasing the abrasion resistance said method comprising the steps of melting 40 parts of partially oxidized polyethylene having a molecular weight of approximately 1200 to 2000 and an acid num ber of 14 to 17, maintaining said molten polyethylene at a temperature of about 230 to 245 F., adding there- 'to and mixing therewith 11 parts of oleic acid heated to -a temperature of 230 F., adding to the mixture 2. 60

percent aqueous solution of 2 parts of potassium hydroxide at 'a controlled rate while constantly stirring said mixture and maintaining the temperature thereof at from 230 to 245 F., adding said mixture to water heated to a temperature of from 200 to 210 F. while stirring said water to form an emulsion, the amount of water in said 7. The method .of increasing the abrasion resistance of surfaces of newly-formed articles of glassware suchas bottles, jars, tumblers and the like by providing an ex tremely thin invisible film thereover, said method comprising the steps of melting 40 parts of partially oxidized low-molecular weight polyethylene, said polyethylene having a molecular weight of approximately 1200 to 1500 and an acid number of 14.to 17, adding 11 parts oleic acid to the molten polyethylene then 2 parts of an alkali emulsion being 207 parts, the polyethylene in said emulsion having a particle size of from 1 to 5 microns, di-

' luting 'said emulson with water, spraying the diluted hydroxide in aqueous solution to the molten polyethylene-oleic acid mixture with constant stirring while controlling the temperature of the emulsion in the range of from 230 to 245 F., adding the formed mixture to water, the total amount of water in the emulsion being 207 parts, the polyethylene in emulsified form having a particle size of less than 10 microns and comprising a solids content of about 20% by weight of the emulsion, diluting the concentrated emulsion with water, and spraying the diluted emulsion over glassware at an elevated temperature of about 400 F. to obtain firm adherence of the emulsified polyethylene particles with elimination of the water component.

8. The method in accordance with claim 7, including polyethylene particles in film form to said surfaces with elimination of the water components therefrom.

"5. The method of forming a concentrated translucent emulsion of polyethylene particles in water, saidpolyethylene particles having a size of less than 10 microns, comprising-the steps of melting 140 parts of partially oxidized polyethylene having a molecular Weight of approximately 1200 to 2000 and an acid number of 14 to 17, maintaining said moltenpolyethylene at a temperature of about 230 to 245 F., adding thereto and mixing therewith 11' parts of oleic acid heated to a temperature of 230 F., adding to the mixture a 60 percent aqueous from 200 to 210 F. While stirring said water to form an: emulsion, the amount of water in said emulsion being 207 parts, and cooling said emulsion,

6. The process as defined in claim 5 'wherein said emulsion is further diluted, with up to 200 parts water.

ethylene with water in the ratio of about to l or more and spraying the diluted emulsion in finely atomized form over the heated glassware to deposit'an adherent invisible film over contacted glass surfaces.

References Cited in the file of this patent UNITED sTATEs PATENTS OTHER- REFERENCES Warth: The Chemstry and Technology of Waxes, pp. 525-530, Reinhold (1956).

Warth: The Chemistry and Technology of Waxes, pp. 447-8, 524-5, 530-4, 571-2, Reinhold (1956). 

1. THE METHOD OF INCREASING THE ABRASION-RESISTANCE OF SURFACES OF NEWLY FORMED ARTICLES OF GLASSWARE SUCH AS BOTTLES, JARS, TUMBLERS AND THE LIKE BY PROVIDING AN EXTREMELY THIN INVISIBLE FILM THEREOVER, SAID METHOD COMPRISING THE STEPS OF MELTING 40 PARTS OF PARTIALLY OXIDIZED LOW-MOLECULAR WEIGHT POLYETHYLENE HAVING A MOLECULAR WEIGHT OF APPROXIMATELY 1200 TO 2000 AND AN ACID NUMBER OF 14 TO 17, ADDING TO THE MOLTEN POLYETHYLENE 11 PARTS OF A FATTY ACID SELECTED FROM THE GROUP CONNSISTING OF OLEIC, PALMITIC, STEARIC, LAUARIC, AND MIXTURES THEREOF, ADDING 2 PARTS OF AN AQUEOUS SOLUTION OF AN ALKALI METAL HYDROXIDE TO THE MOLTEN POLYETHYLENE-FATTY ACID MIXTURE WITH CONSTANT STIRRING WHILE CONTROLLING THE TEMPERATURE OF THE MIXTURE WITHIN THE RANGE OF FROM 230* TO 245* F., ADDING SAID MIXING TO WATER TO FORM AN EMULSION, THE TOTAL AMOUNTS OF WATER IN SAID EMULSION BEING 207 PARTS, THE POLYETHYLENE IN SAID EMULSION HAVING A PARTICLE SIZE OF LESS THAN 10 MICRONS AND COMPRISING A SOLIDS CONTENT OF ABOUT 20% BY WEIGHT OF THE EMULSION, DILUTING SAID EMULSION WITH WATER, AND SPRAYING THE DILUTED EMULSION OVER GLASSWARE AT A TEMPERATURE SUBSTANTIALLY BELOW THE ANNEALING TEMPERATURE OF SAID GLASSWARE TO OBTAIN A FIRM ADHERENCE OF THE EMULSIFIED POLYETHYLENE PARTICLES IN FILM FORM TO SAID SURFACES WITH ELIMINATION OF THE WATER COMPONENT THEREFROM, ALL OF SAID PARTS BEING BY WEIGHT. 